CA2048042A1 - Process for the preparation of insecticidal acaricidal and nematicidal 2-aryl-5-(trifluoromethyl) pyrrole compounds - Google Patents

Process for the preparation of insecticidal acaricidal and nematicidal 2-aryl-5-(trifluoromethyl) pyrrole compounds

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Publication number
CA2048042A1
CA2048042A1 CA002048042A CA2048042A CA2048042A1 CA 2048042 A1 CA2048042 A1 CA 2048042A1 CA 002048042 A CA002048042 A CA 002048042A CA 2048042 A CA2048042 A CA 2048042A CA 2048042 A1 CA2048042 A1 CA 2048042A1
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Prior art keywords
compound
preparation
alkyl
base
trifluoromethyl
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French (fr)
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Roger W. Addor
Joseph A. Furch
David G. Kuhn
Kenneth A. M. Kremer
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BASF SE
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Priority claimed from US07/560,396 external-priority patent/US5030735A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/14—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/10—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and halogen atoms, or nitro or nitroso groups, bound to the same acyclic carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/16—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pyrrole Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

31,410 PROCESS FOR THE PREPARATION OF INSECTICIDAL, (TRIFLUOROMETHYL) PYRROLE COMPOUNDS

ABSTRACT OF THE INVENTION

There is provided a process for the prepara-tion of 2-aryl-5-(trifluoromethyl)pyrrole compounds which are useful as insecticidal, acaricidal and nematicidal agents. l,l,1-trifluoro-2-propene compounds which are useful in the preparation of the above arylpyrrole compounds and a method for their preparation are also described.

Description

31,410 2 ~

PROCESS FOR THE PREPARATION OF INsEcTIcTn ACARICIDAL_~ND N~MATICID L 2-ARYL-5-(TRIFLUOROMETHYL~PYRROLE COMPOUNDS

BACKGROUND OF THE INVENTION

It is an object of the present invention to provide a more efficient process for the preparation of insecticidal, nematicidal and acaricidal 2-aryl-5-(tri-fluoromethyl)pyrrole compounds which reduces excess starting materials and reaction time and increases product yield.
It is a further object of the invention to provide an efficient method of preparing the 1,1,1-trifluoro-2-propene compounds of the present invention.

SUMMARY OF T~E INVENTION
The present invention relates to a process for the preparation of insecticidal, nematicidal and acaricidal 2-aryl-5-(trifluoromethyl)pyrrole compounds of formula I

W Y
F 3 C ~ J M

( I ) wherein W is C1-C~ alXyl, CF3 or H;
Y is CN, NO2 or C02R;
R is Cl-C~ alkyl;
L is H, F, Cl or Br;
M is H, F, Cl, Br, I, CF3, NO2 or OR1; and R1 is C1-C3 alkyl or C2F4H by a single step reaction between an azalactone compound of formula II

0~ L
F3ClN~ ~1 (Il~
wherein L and M are as described above and an ~-halo-~,~-unsaturated nitrile, ester or nitro compound of formula III

C C
U X
(III~
wherein W and Y are as described above; X is Cl, Br, I
or and the cis and trans isomers thereof in the presence of a polar solvent and a base.

~ 2 ~ 3 DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a process for the preparation in good yield of insecticidal, nematicidal and acaricidal compounds of formula I

W Y

F3C ~ I ~ M

(I) wherein W is Cl-C4 alkyl, CF3 or H;
Y is CN, NO2 or C02R;
R is Cl-C4 alkyl;
L is H, F, Cl or Br;
M is H, F, C1, Br, I, CF3, NO2 or OR1; and Rl is Cl-C3 alkyl or C2F4H by an efficient single step reaction between an azalactone compound of formula II
~4 L

F3C 1 N ~ M

(Il) wherein L and M are as described above and an ~-halo-~,~-unsaturated nitrile, ester or nitro compound of formula III

H Y

C-- C
I~ X
(III) wherein W and Y are as described above; X is Cl, Br, I
or and the cis and trans isomers thereof in the presence of a polar solvent and a base.
The process preferably comprises reacting a formula II azalactone as described above with at least about one molar equivalent, preferably about one to five molar equivalents, of a formula III ~-halo~
unsaturated nitrile, ester or nitro compound as described above and at least about one molar equiva-lent, preferably about one to five molar equivalents, of a base in the presence of a polar solvent preferably at a temperature range of about 20C to 180C to form 2-aryl-5~(trifluoromethyl)pyrrole compounds of formula I. Naturally, it is especially preferred to use as little excess reactants as possible. Advantageously, stoichiometric quantities may be used in the present invention and still maintain good yields.
The product formula I compounds may be isolated by conventional techniques such as dilution of the reaction mixture with water and ~iltration of the formula I product or extraction of said product with a suitable solvent. In the isolation procedure any suit-able extraction solvents may be employed, including water-immiscible solvents such as ether, ethyl acetate, methylene chloride and the like.
Bases suitable for use in the process of the invention include bases such as alkali metal carbonates, Cl-C4 trialkylamines, alkali metal hydroxides and pyridine. Preferred bases are pyridine, triethylamine and sodium carbonate.

Reaction solvents suitable for use in the above process include any polar solvents, Por example solvents such as acetonitrile, dimethylsulfoxide, dimethylformamide, ethanol, methanol and isopropanol.
Acetonitrile and dimethylformamide are preferred reaction solvents.
Certain starting formula III compounds are described below.
The 1,1,1-trifluoro-2-propene compounds of the present invention have the structural formula IIIa:

H Z
C--C

(IIIa) wherein Z is Cl, Br or I;
Y is CN, C02R or C(O~R1;
R and Rl are hydrogen or C1-C4 alkyl; and the cis and trans isomers thereof.
Preferred 1,1,1-trifluoro-2-propene compounds of the invention are those in which X is Cl or Br; Z is CN
or C(O)R1; and Rl is Cl-C4 alkyl.
Formula IIIa compounds may be prepared by reacting trifluoroacetaldehyde with (triphenylphos-phoranylidene)acetonitrile in a solvent to give 4,4,4-trifluorocrotononitrile. The said 4,4,4-trifluoro-crotononitrile or other compound having the structural fsrmula IV:

H H
C - C

(IV) ~ qi _ ~., .. , ;~

wherein Z is CN, C02R, C(O)R1;
R and Rl are C1-C4 alkyl; and the cis and trans isomers thereof;
is reacted with at least about two molar equivalents, preferably about two to five molar equivalents of a halogenating agent in the presence of a solvent to form 2,3-dihalo-1,1,1-trifluoropropane compounds of formula V:

(V) wherein X is Cl, Br or I; and Z is as described above.
Halogenating agents that may be employed include bromine, chlorine, iodine, and the like. Reaction solvents suitable for use in the above-described reaction include tetrahydrofuran, carbon tetrachloride and the like. The resultant 2,3-dihalo-1,1,1,-trifluoropropane is then reacted with at least about one molar equivalent, preferably about one to three molar equivalents, of a base in the presence of a solvent to form l,1,1-trifluoro-2-propene compounds of formula I. Bases suitable for use in the reaction include triethylamine, pyridine and sodium carbonate and the like. Solvents such as ether and tetrahydrofuran may be preferably employed. This reaction scheme is illustrated as follows:

H H H Z
C - C\ - ~ CF3CHXCHXZ ~ C C

(IV) (V) (IIIa) ~ 3 2 The preparation of formula IIIa compounds was illustrated in the previous reaction scheme, except when R is hydrogen. To prepare the formula IIIa compounds when R is hydrogen an additional hydrolysis step may be required. Hydrolysis of a formula IIIa compound wh~n R is not hydrogen yields another formula IIIa compound having the same structure except that R
is now hydrogen.
In order to facilitate a further understand-ing of the invention, the following examples are presented to illustrate more specific details thereof.
The invention is not to be limited thereby except as defined in the claims.

Preparation of 2-Phenyl-5-~trifluoromethyl)pyrrole-3-carbonitrile in the presence of a base.

O CN
0~ /
F3ClN~ + H2C = C + N(CH2CH3)3 CN

Triethylamine (4.5g, 0.044 mol) is added dropwise to a mixture of 4-phenyl-2-(trifluoromethyl)-5(2H)-oxazolone (lO.Og, 0.043 mol), 2-chloroacrylo-nitrile (3.51g/ 0.43 mol) and acetonitrile (50 mL).

- g The temperature of the reaction mixture rises to 65~
and carbon dioxide gas evolves during the addition.
After the addition is complete the reaction mixture is heated at reflux temperature for one hour, cooled to room temperature and poured into water (150 mL). The solids are collected by filtration, air-dried and dried under vacuum at 60C to give the title compound as a white solid (10.05g, 97~. Identified by NMR spectral analyses.
The process described affords a nearly quantitative yield of the product pyrrole using stoichiometric amounts of reagents and short reaction time.
EXAMPLE ?
Preparation of 2-Phenyl-5-(trifluoromethyl~pyrrole-3-carbonitrile w thGut added base 0~ /
F3C--~N~3 + H2C = C +

CN

F~C ~

4-Phenyl-2-(trifluoromethyl)-5(2H)-oxazolone (13.5g, 0.059 mol), 2-chloroacrylonitrile (26 mL, 0.295 mol) and acetonitrile (250 mL) are heated at reflux temperature for 52 hours. The reaction mixture is then cooled to room temperature and concentrated in vacuo to give a solid. Recrystallization of the solid from toluene gives the title product as a yellow solid (10.lg, 73~). Identified by NNR spectral analyses.

The procedure without added base gives only a 73% yield of the title product despite the use of a large excess of 2-chloroacrylonitrile and a long reaction time.

Preparation of Methyl 2-(p-chlorophenyl)-5-(trifluoro-methyl)pyrrole-3-carboxylate ~ / N(CHzCH3)3 F3C 1 N + H2C = C CH3CN

~ C1 Triethylamine (5.5gg, 0.055 mol) is added dropwise to a mixture of 4-(p-chlorophenyl)-2-(tri-fluoromethyl~-5(2H)-oxazolone (15.6g, 0.054 mol), methyl ~-chloroacrylate (6.52.g, 0.054 mol) and aceto-nitrile ~50 mL). The reaction mixture heats up to 55 C
during the addition. After the addition is complete, the reaction mixture is heated at reflux temperature for one hour, cooled to room temperature and filtered.
The filtrate is poured into an ether/water mixture and extracted with ether. The combined organic extracts are dried over anhydrous magnesium sulfate and concen-trated in vacuo to give a black residue. Recrystall-ization of the residue from hexane gives the titlecompound as an orange solid (8.25g, 50.2%). Identified by NMR spectral analyses.

Preparation Usin~ Non--Polar Solvent Instead of Polar Solvent This example shows th~ necessity of using a polar solvent. Surprisingly, the base-catalyzed reaction when run in the presence of a non-polar solvent such as toluene does not result in the desired pyrrole.

O CN
~4 /
F3ClN~3 ~ H2C = C
Cl ~ CN

2-chloroacrylonitrile ~3.85g, 0.044 mol) is added to a 0C mixture of 4-phenyl-2-(trifluoromethyl)-5(2H)-oxazolone (lO.Og, 0.044 mol~ and toluene (50 mL).
Triethylamine (4.49g, 0.044 mol) is added dropwise to the reaction mixture and the temperature rises to 25C.
When the addition is complete, water is added to the reaction mixture and the layers are separated~ The organic layer is dried over anhydrous magnesium sulfate and concentrated in vacuo to give alpha-chloro-5-oxo-4-phenyl-2-(trifluoromethyl)-3-oxazoline-2-propionitr-ile as an amber liquid (8.37g, 60%). Identified by NMR
spectral analyses.

This example demonstrates that with the addition of a base and a polar solvent s-lch as acetonitrile to the product formed in Example 4 the desired pyrrole is formed.
o 0~/
F :3 C ~N~ N ( C H Z C H 3 ) 3 ---' \~_ C N

CN

Triethylamine ~0.077g, 0.76 mmol) is added dropwise to a refluxing mixture of alpha-chloro-5-oxo-4-phenyl-2 (trifluoromethyl)-3-oxazoline-2-propioni-trile (0.24g, 0.76 mmol) and acetonitrile (25 mL). The reaction mixture is refluxed for 2 hours, cooled to room temperature and poured into water. The solids are collected by filtration and dried to give the title compound as a white solid (0.16g, 88~). Identified by NMR spectral analyses.

_XAMPLh~ 6 Solvent and base effects upon 2-aryl-5-(trifluoro-methvl)pyrrol~ formation The effects of solvent and base changes on the synthesis of 2-phenyl-5-(trifluoromethyl)pyrrole-3-carbonitrile from 4-phenyl-2-(trifluoromethyl)-5(2H)-oxazolone and 2-chloroacrylonitrile are shown in Table I. The percentages shown represent area percent determined by HPLC analysis of the reaction mixture after refluxing for 1/2 hour.

TABLE I
Solv t and Base Effects % Yield Solvent Base _Arylpyrrole Toluene Triethylamine 11 Toluene Pyridine 8 ~etrahydrofuran Triethylamine 39 ~thanol Triethylamine 80 Acetonitrile Triethylamine 96 Acetonitrile - 4*
Dimethylformamide Pyridine 100 ~imethylformamide Sodium carbonate 74 Dimethylformamide Triethylamine 100 * 1 hour refluxing Base effects in 2-aryl-5-(trifluoromethyl)pyrrole formati~n Base effects on the synthesis of 2-aryl-5-(tri-fluoromethyl)pyrroles are shown in Table II. Acetonitrile is the solvent in all reactions.

~:S
a~
.~ a~ ~D ~ O t` O
~ r~
o~

J ~
~ CO ~ ~P ~ ~ ~1 ~ ~ t`~ ~

~ I
`~, Z~
~/ ~ I
U~ l I
> ~ O ~ O ~1 0 ~1 ~
H ~ I
I
11 ~0 h +) xi I o c~ m m c~
X ~
h ~1 h 1~\ (~, o / ~ ~ ~ ~
I ~ ~ ~

X X

O O
~1 ~1 ~i ~1 +J ~
O O C~ ~ O O
I I I I ~ ~
h h O O
X X
X X C > C~ X 1~

EX~MPLE 8 Sol~ent effects in 2-arYl-5-(trifluoromethyl~pyrrole forma-tion Solvent effects in the formation of 2-(p-chloro-phenyl-5-(trifluoromethyl)pyrrole-3-carbonitrile from 4-(p-chlorophenyl)-2-(trifluoromethyl)-5(2H)-oxazolone and 2-chloroacrylonitrile are shown in Table III.

TABLE III
Solvent effects in 2-aryl-5-(trifluoro-~ethyl)pyrrole formation Equivalents of 2-Chloroacrylo- %
_Solvent nitrile Time Yield Nitromethane 10 21 14 Toluene 10 17 17 Trifluoroacetic Anhydride 10 17 17 Acetonitrile 10 17 46 a Hours reaction mixture is refluxed The results of these experiments show that even with polar solvents and long times, yields are generally poor in the absence of added base.

Preparation of 4.4,4-Trifluorocrotononitrile ~E)-and(Z)-Trifluoroacetaldehyde (47.4g, 0.48 mol),generated by addition of 1-ethoxy-2,2,2~trifluoro-ethanol (77.6g, 0.48 mol) to polyphosphoric acid (300 mL) heated to 150-180C, is swept with nitrogen over 2 hours into a slurry of (triphenylphosphoranylidene) -15~ 3 ~

acetonitrile (97.3g, 0.32 mol) in ether (400 mL). The reaction mixture is stirred overnight under nitrogen.
After filtering off the solid triphenylphosphine oxide, the ether is distilled off to obtain an orange solu-tion. Bulb to bulb distillation of the solution affords 2 fractions of the title compound as a clear colorless oil (14.3g, 37%). Fraction 1 (bp 20-40C , 14mm) contains a 6:1 mixture of (E):(Z). Fraction 2 (bp 40-50C, 14mm) contains a 2:1 mixture of (Z):(E).
The fractions are identified by NMR analyses.

Preparation cf 2,3-Dibromo-4 t 4.4-Trifluorobutyronitrile F3C H Br CN
I I
C_C\ + Br2 F3C--C--C--H
H CN H Br (E~ and (Z) Bromine (4.57g, 0.029 mol) is added over a 5 minute period to a solution of 4,4,4-trifluorocrotono-nitrile (3.46g, 0~029 mol) and carbon tetrachloride (70 mL). The resulting dark red solution is refluxed for 5 hours, then water (70 mL) is added to terminate the reaction. The organic layer is separated, washed sequentially with water, 5% sodium thiosulfate solution and water, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to yield the title product as a yellow oil (6.1g, 76%), identified by NMR
spectral analyses.
Following the procedure of example 10, but substituting the appropriately substituted 1,1,1-tri-fluoro-2-propene for 4,4,4-trifluoro~rotononi--16- ~3 i ~ i ?!

trile yields the following compounds.

Br Z
F
H Br Z State o COCH2CH3 c o l or 1 ess o i 1 o Il CCH3 yel low oi 1 CH yel low oi 1 ~X~MPLE 11 Preparation of 2-Bromo 4~4,4-_ rifluorocrotononitrile fE)- and (Z)-Br CN F3C Br I I \ /
F3C--F--F--H ~ N(CH2CH3)3 ~ C C\
H Br H CN

(E) and (Z) Triethylamine (3.7g, 0.037 mol) is added dropwise to a solution of 2,3-dibromo 4,4,4-trifluoro-butyronitrile (5.32g, 0.023 mol) and tetrahydrofuran (100 mL). A voluminous white precipitate forms during the addition. Stirring is continued for 1 hour, then the solid is filtered off and washed with tetrahydrofuran. The tetrahydrofuran is distilled off to give a dark brown oil. Bulb to bulb distillation (15 mm, 24C) of the oil yields the title product as a clear colorless liquid (3.lg, 32%). MMR spectral analyses identifies a 6:1 mixture of E:Z .
Following the procedure described in example 11, but using the appropriately substituted 1,2-di-bromo-3,3,3-trifluoropropane for 2,3-dibromo-4,4,4-tri-fluorobutyronitrile yields the compounds shown below.

F3C Br C--C
H Z
(E~ and (Z) Z State -Il COCHzCH3 c 1 ear ye 11 ow o i 1 o CCH3 red o i 1 Preparation of 2-(p-chlorophenyl~-4.5-bis(trifluoro-methyl~pyrrole-3-carbonitrile F3C\ Br F3C y 0 ~ 0 C_C +N~ t N(CHzCH3)3 H CN
(E) and (Z) \~
Cl 4-(p-Chlorophenyl)-2-(trifluoromethyl)-2-oxazolin-5-one (2.0g, 7.59 mmol) and 2-bromo-4,4,4-tri-fluorocrotononitrile (0.81g, 4.05 mmol) are dissolved in acetonitrile (lO mL). To the resulting yellow solution triethylamine (0.45g, 4.46 mmol) is added dropwise while the reaction flask is cooled with a water bath. After stirring at 25C overnight, the reaction mixture is poured into water. The aqueous layer is extracted with ethyl acetate and the combined organic extracts are washed sequentially with water, 5%
sodium thiosulfate solution and brine, dried over anhydrous magnesium sulfate and concentrated in vacuo to give a yellow solid. The solid is chromatographed using silica gel and eluted with hexane/ethyl acetate 3:1 to yield the title compound as yellow crystals (1.26g, mp 208C).
Following the procedure of example 12, but substituting 3-bromo-5,5,5-trifluoro-3-penten-2-one for 2-bromo-4,4,4-trifluorocrotononitrile yields 2-(p-2 ~

chlorophenyl~-4,5-bis (trifluoromethyl)pyrrol-3-yl methylketone as yellow crystals.

Preparation of Ethyl 2-(p-chloro~henyl)- 4.5-bis ttrifluoromethyl)pyrrole-3-c_boxylate F3C\ Br F3C <~5~0 C=C\ + N~ t N(CH2CH3~3 ~E) and ~Z) Cl o F3C~ OCH2CH ~
F3C--~N~3__ H Cl Triethylamine (l.lg, 0.011 mol) is added dropwise to a solution of 4-(p-chlorophenyl)-2-(tri-fluoromethyl3-2-oxazolin-5-one (2.64g, 0.01 mol) and acetonitrile ~25 mL). After stirring for 10 minutes at room temperature, a solution of ethyl 2-bromo-4,4,4-trifluorocrotonate (2.47g, 0.01 mol) and acetonitrile (1 mL) is added dropwise to the reaction mixture. The reaction mixture is stirred at room temperature for 2 hours then poured into water and extracted with ethyl acetate. The combined organic extracts are washed sequentially with water and brine, dried over anhydrous magnesium sulfate and concentrated in vacuo to give an orange oil which solidifies upon standing. Trituration with hexanes gives the title product as a yellow solid (2.3~g, 6~.3%, mp 138-140c).

Preparation of 2-(3,4-dichlorophenyl)-4,5-bis(tri-fluoromethyl)pyrrole-3-carbonitrile Br CN F3C ~
F3C--C--C-- H + N ~ + N(CH2CH3)~
I I ~
H Br ~ Cl C CN
~ Cl F3C ~ N ~ Cl Txiethylamine (0.59g, 5.83 mmol) is added dropwise to a solution of 2,3-dibromo-4,4,4-trifluoro-butyronitrile (1.63g, 10.2 mmol) and tetrahydrofuran (20 mL). Stirring is continued for 15 minutes then a solution of 4-(3,4-dichlorophenyl)-2-(trifluoromethyl)-2- oxazlin-5-one (2.6g, 8.72 mmol), triethylamine (0.38g, 8.7 mmol) and acetonitrile (5 ml) is added dropwise to the reaction mixture. The reaction mixture is stirred overnight at room temperature, poured into water and extracted with ethyl acetate. The combined organic extracts are washed sequentially with water and brine, dried over anhydrous magnesium sulfate and concentrated in vacuo to give a brown oil. Chro-matography of the oil using silica gel and hexanes/
ethyl acetate 3:1 yields the title product as a pale yellow solid (1.49g, 67%, mp 205-2Q8C).

Claims (10)

1. A process for the preparation of a first compound having the structural formula:

wherein W is C1-C4 alkyl, CF3 or H;
Y is CN, NO2 or CO2R;
R is C1-C4 alkyl;
L is H, F, Cl or Br;
M is H, F, Cl, Br, I, CF3, NO2 or OR1; and R1 is C1 C3 alkyl or C2F4H which comprises reacting a second compound having the structure wherein L and M are as described above with at least about 1 molar equivalent of a third compound having the structure wherein W and Y are as described above, X is C1, Br, I
or and the cis and trans isomers thereof in the presence of at least about 1 molar equivalent of a base and a polar solvent to form said first compound.
2. The process according to Claim 1 wherein the base is an alkali metal carbonate, C1-C4 trialkyl-amine or pyridine, and the polar solvent is acetoni-trile, dimethylformamide, dimethylsulfoxide, ethanol, methanol or isopropanol.
3. The process according to Claim 2 wherein the base is triethylamine.
4. The process according to Claim 2 wherein the polar solvent is acetonitrile.
5. The process according to Claim 2 wherein the temperature of the reaction mixture is about 20° to 180°C
6. A compound having the structure:

wherein X is Cl, Br or I;
Z is CN, CO2R or C(O)R1;
R and R1 are hydrogen or C1-C4 alkyl; and the cis and trans isomers thereof.
7. The compound according to claim 6, wherein X is Cl or Br; Z is CN or C(O)R1;
and R1 is C1-C4 alkyl.
8. The compound according to claim 7, 3-bromo-5,5,5-trifluoro-3-penten-2-one or 2-bromo-4,4,4-trifluorocrotononitrile.
9. A method for the preparation of a first compound having the structure:

wherein X is Cl, Br or I;
Z is CN, CO2R or C(O)R1;
R and R1 are C1-C4 alkyl; and the cis and trans isomers thereof which comprises reacting a second compound having the structure wherein Z is as described above; and the cis and trans isomers thereof with at least about 2 molar equivalents of a halogenating agent in the presence of a solvent to yield an intermediate compound having the structure wherein X and Z are as described above and reacting said intermediate with at least about one molar equiva-lent of a base in the presence of solvent to form said first compound.
10. The method according to Claim 9, wherein the base is triethylamine, pyridine or sodium carbon-ate; the halogenating agent is bromine or chlorine; and the reaction solvent is tetrahydrofuran, carbon tetrachloride or ether.
CA002048042A 1990-07-31 1991-07-29 Process for the preparation of insecticidal acaricidal and nematicidal 2-aryl-5-(trifluoromethyl) pyrrole compounds Abandoned CA2048042A1 (en)

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US07/560,396 1990-07-31
US07/560,403 1990-07-31
US07/560,403 US5068390A (en) 1990-07-31 1990-07-31 1,1,1-trifluoro-2-propene compounds
US07/560,396 US5030735A (en) 1990-07-31 1990-07-31 Process for the preparation of insecticidal, acaricidal and nematicidal 2-aryl-5-(trifluoromethyl) pyrrole compounds

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US5128485A (en) * 1990-12-17 1992-07-07 American Cyanamid Company Synthesis of 2-aryl-5-(trifluoromethyl)pyrroles useful as pesticidal agents and as intermediates for the preparation of said agents
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CN102584667B (en) * 2011-12-21 2013-12-18 湖南化工研究院 Arylpyrrole compound with biological activity and preparation method thereof
MX2019010998A (en) * 2017-03-13 2019-10-17 Basf Agro Bv Production of arylpyrrol compounds in the presence of dipea base.
CN112608268A (en) * 2020-12-22 2021-04-06 李通 Method for producing chlorfenapyr intermediate pyrrole by using solvent DMF to replace acetonitrile
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US5010098A (en) * 1987-07-29 1991-04-23 American Cyanamid Company Arylpyrrole insecticidal acaricidal and nematicidal agents and methods for the preparation thereof
CN1026206C (en) * 1987-07-29 1994-10-19 美国氰胺公司 Arylpyrrole insecticidal acaricidal and nematicidal agents and method for preparation thereof
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HU209916B (en) 1994-11-28
JPH04270263A (en) 1992-09-25
CN1058587A (en) 1992-02-12
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DE69107546D1 (en) 1995-03-30
IE912674A1 (en) 1992-02-12
PT98477B (en) 1999-09-30
EP0469262A3 (en) 1992-07-01
IE67178B1 (en) 1996-03-06
GR3015204T3 (en) 1995-05-31
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SK280894B6 (en) 2000-09-12
IL98235A0 (en) 1992-06-21
AU646480B2 (en) 1994-02-24
CZ285271B6 (en) 1999-06-16
CN1030699C (en) 1996-01-17
PT98477A (en) 1992-05-29
ATE118766T1 (en) 1995-03-15
CN1119184A (en) 1996-03-27
BR9103255A (en) 1992-02-18
DE69107546T2 (en) 1995-09-28
EP0469262A2 (en) 1992-02-05
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